Rosin derivatives



ams no. a o 2,437,431

UNITED STATES PATENT OFFICE BOSIN DERIVATIVES Alfred L. Rummelaburz, New Castle. DeL, aasignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 21, 1948, Serial No. 656.166

6 Claims. (01. 260-97) 2 l This invention relates to new cyclohexanols had an acid number of 62: hydroxyl content of and more particularly'to rosin-substituted cyclo- 4.7% and color of X on the rosin color scale. hexanols and to a method of producing them. Example H While many substituted cyclohexanols have been prepared in the past, none have been pre- 5 A solution Of 453 parts methyl abietate in v pared containing a resin acid substituent. 3 par o benzene was added during Now in accordance with this invention it has at ill-20 C. to an agitated Solut on 0 p t been found that new substituted cyclohexanols, boron trifl oride in a i re of 453 Darts 01 the rosin-cyclohexanols and rosin ester-cyclophenol in 333 p s o b e it tio wa hexanols, may be prepared by the catalytic hy- 10 continued at 2030 C. 102 8. period Of 2 hours. drogenation of rosin-phenols or rosin ester- The reaction mixture was water-washed to rephenols. These new cyclohexanols which are move the catalyst after which the solvent was substituted by a, rosin or rosin ester are unique removed by distillation. A yield of 528 parts of in that they contain not only a reactive hydroxyl the rosin ester-p e ol a i a color of F group in t eyclohexyl i l, t also nt 1 the rosin color scale, an acid number oi 5, and the original carboxyl or ester group of the rosin a p o c hydroxyl content O 33% was radical. As a result they undergo many reactions t such as further reduction, esterification, etherifity parts o t e above o n e eno n cation, etc., to provide a whole series of new com- 150 Pa s O ol o fl W88 y o ated in 8 pounds. They are l light-colored resins which 20 stainless steel autoclave at 170 C. in the presence are valuable for many purposes as such. 0f 20 Parts Of Rene? nickel catalyst t a hydro- The following examples are illustrative of the gen P r of 2000-2675 po nds per square inch. new cyclohexanols and of the method of preparfor a P of about hours- About 036% ing them. All parts and percentages are by hydro n wa absorbed- The was weight unless otherwise specified. filtered and then evaporated to remove the solvent. The rosin ester-cyclohexanol which re- Erample I mained as a residue had an acid number oi 2.6; a hydroxyl content of 3.2%: melting point of A s l t of 1370 pa t of N w d rosin in 1000 65 C. and a color of W on the rosin color scale. parts of benzene was added to an agitated solu- Th rosin-phenols or rosin ester-phenols, tion of 60 parts of boron trifiuoride in a mixture which are hyd ogen t d in accordance with this of 1350 parts of phenol and 750 parts of benzene, invention, are prepared by condensing rosin or th temp r being h l at during rosin esters with phenols using a catalyst which the addition- The mixture was then agitated for will promote the formation of substituted phenols ho lrs at h ly Was removed rather than phenol ethers. Suitable catalysts by washing the reaction mixture with water at for t purpose ar boron trifluoride and hydro- 50-60" C. and the benzene and excess phenol were gen fluoride, Any rosin material such as wood removed by distillation. The rosin-phenol which m, gum i polymerized rosin, isomerlzed i e as a id e amounted o 17.85 parts rosin, heat-treated rosin, may be used for the This rial h a phenolic hydroxyl content of 40 preparation of the rosin-phenols. Likewise, the as determined by the Zerewitimfi method esters of these rosins such as the methyl, ethyl, theory 4.3%) an acid number of 55; a melting glycerol, etc., esters may be used for the preparapoint of 140 C. and a color of F on the rosin color ti n f the rosin ester-phenols. If desired, the

scale. pure resin acids such as the abietic-type and The above rosin-phenol was hydrogenated by pimaric-type acids or the esters of the resin acids d in 60 par s of it in 1500 P r of cyclomay be utilized in place of the rosin or rosin ester hexane and hydrogenating at a temperature of for the preparation of these substituted phenols. 220-225 C. and hydrogen pressure of 2000 to The substituted phenols may be prepared from 2900 pounds per square inch for 12 hours in the any phenols such as phenol, cresol, butyl phenol. presence of 20 parts of Raney nickel as catalyst. amyl phenol, dialkylhydroxy benzenes, dlhydroxy About 1.77%hydrogen was absorbed (theory for benzenes, naphthols, chlorophenols. nitrothe three double bonds in the phenolic end of the phenols, etc., or alkoxyphenols such as guaiacol, condensate is 1.52%). The solution was filtered etc. i

and the solvent removed by distillation. The The hydrogenation of the rosinand rosin rosin-cyclohexanol which remained as a residue ester-phenolsis desirably carried out in solution.

The substituted phenol is dissolved in a suitable inert solvent and the solution is then contacted with hydrogen at pressures of from about 40 to 5000 pounds per square inch in the presence of a hydrogenation catalyst. The hydrogenation may be carried out in a continuous or batchwise process. If desired, the hydrogenation may be carried out using molten rosin without the presence of a solvent.

Suitable solvents for the hydrogenation reactionare the inert or neutral solvents such as methanol, ethanol, butanol, diethyl ether, isopropyl ether, cyclohexane, hexane, ectanes, gasoline, etc.: however, an organic acidic solvent such as acetic acid may be used. Obviously the solvent used is dependent upon the catalyst employed since it must be inert to the catalyst to prevent destruction of the catalyst. Solvents such as acetic acid, ethers and alcohols are most suitable with the noble metal catalyst. In the case of the nickel and copper chromite catalysts, acetic acid cannot be employed as the solvent because of its reaction with the catalyst, and the inert solvents must be used.

Any active hydrogenation catalyst may be used ion: the hydrogenation reaction in accordance with this invention, as for example, a noble metal catalyst such as Adams platinum oxide, reduced platinum, reduced palladium, or an active base metal catalyst such as reduced nickel, Raney nickel and copper chromite. The catalyst may be supported, if desired, on a suitable support such as pumice, kieselguhr, silica gel, carbon, etc. When platinum and palladium catalysts are employed, hydrogen pressures of from atmospheric pressure to below 1000 pounds per square inch and temperatures below 100 C. to about 25 C. may be employed. However, in the case of the nickel and copper chromite catalysts, temperatures of from about 125 C. to 250 C. may be utilized as well as hydrogen pressures of above 100 pounds per square inch, preferably about 700 to 5000 pounds per square inch. One of the most preferable catalysts for the hydrogenation reaction in accordance with this invention is Raney niekehhydrogen pressures of about 500 to 3000 pounds per square inch and temperatures of about 125 C. to about 250 C. being used.

Following the hydrogenation step, the reaction mixture is cooled, removed from the hydrogenation vessel and filtered to separate the catalyst. The solution is then evaporated to remove the solvent, the evaporation desirably taking place under reduced pressure. However, the solvent may be removed by steam distillation or a combination of steam and vacuum distillation. The rosinor rosin ester-cyclohexanol will remain as a residue by this procedure.

The rosinand rosin ester-cyclohexanols are amorphous, light-colored resins having melting points between 50 C. and 150 C. They cannot be readily distilled even under reduced pressure. In general, they have a color of WW to X on the rosin color scale as compared to a color of D to F of the corresponding rosinand rosin ester-phenols.

The rosinand rosin ester-cyclohexanols may be subjected to further hydrogenation to saturate the remaining double bond in the rosin substituent. The hydrogenation of the rosin group may be carried out directly following the hydrogen- 4 continuing the hydrogenation tor a longer period or time. Either the original catalyst or fresh catalyst may be employed. In the case of the rosin-cyclohexanols, the hydrogenation may also be continued to reduce the carboxyl group or the rosin substituent to an alcoholic group, thereby producing a compound containing a reactive hydroxyl group in both the cyclohexyl radical and the rosin radical. In this case, a catalyst such as reduced copper chromite is desirable. I

The rosinand rosin ester-cyclohexanols may be sulfated to form wetting agents and deteration of the aromatic phenol ring if desired by gents. The rosin-cyclohexanols may also be reacted with monoand poly-basic acids to form resinous esters which in turn may be esterified at their carboxyiic groups with monoand polyhydric alcohols to .form products suitable for use as plasticizers and resins for coatings and adhesives. The rosinand resin ester-cyclohexanols may be oxidized with nitric acid, etc., to form substituted adipic acids which are dibasic acids useful in preparing alkyd resins, etc. The rosin-cyclohexanols may also be used for preparing modified alkyd resins by esterifying the carboxyl group with a polyhydric alcohol and esterifying the secondary hydroxyl group with a suitable unsaturated fatty acid such as the soybean, linseed, dehydrated caster. tung..

etc., fatty acids.

What I claim and desire to protect by Letters Patent is:

1. A cyclohexanol selected from the group consisting of rosinand resin ester-cyclohexanols.

. 2. Arosin-cyclohexanol.

3. A rosin ester-cyclohexanol.

4. The process of preparing a cyclohexanol which comprises contacting a solution or a substituted phenol, selected from the group consisting of rosin-phenols and rosin ester-phenols, in a solvent at a temperature of from about 25 C. to about 250 C. with hydrogen in the presence of a hydrogenation catalyst.

5. The process of preparing a cyclohexanol which comprises contacting a solution of a substituted phenol, selected from the group consisting of rosin-phenols and rosin ester-phenols, in an inert solvent at a temperature of about 25 C. to about 250 C. with hydrogen under a pressure of from atmospheric pressure to about 5000 pounds per square inch in the Presence 01 ALFRED L. RUMME'LSBURG.

REFERENCES CITED The following references are of record in the file of this patent: I

v UNITED STATES PATENTS Number Name Date Humphrey June 21, 1938 I Certificate of Correction I w Patent No. 2,437,481. v March 9, 1948.

ALFRED L. RUMMELSBURG It is hereby certified that error appears in the printed specification of the above numbered patent reqluiring correction as follows: Column 2, line 35, for theword phenol read pheny and that the said Letters Patent shouldbe read with this gorection therein that the same may conform to the record of the casein the Patent Signed and sealed this27th day of April, A. D. 1948.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

